CN115873458A - Aqueous coating liquid, method for producing same, and gas barrier film - Google Patents
Aqueous coating liquid, method for producing same, and gas barrier film Download PDFInfo
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- CN115873458A CN115873458A CN202310003889.8A CN202310003889A CN115873458A CN 115873458 A CN115873458 A CN 115873458A CN 202310003889 A CN202310003889 A CN 202310003889A CN 115873458 A CN115873458 A CN 115873458A
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- layer
- gas barrier
- water
- linking agent
- aqueous coating
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- 238000000576 coating method Methods 0.000 title claims abstract description 162
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Abstract
The invention discloses an aqueous coating liquid, a preparation method thereof and a gas barrier film. The aqueous coating liquid comprises 100 parts by weight of water-soluble polymer, 10-150 parts by weight of siloxane hydrolysate and nano oxide, 0.1-20 parts by weight of first cross-linking agent, 0.1-10 parts by weight of second cross-linking agent and 1000-12000 parts by weight of solvent, wherein the first cross-linking agent comprises covalent cross-linking agent, and the second cross-linking agent comprises dynamic cross-linking agent. The aqueous coating liquid has the advantages of good stability, strong coatability and environmental friendliness, and the formed coating has excellent gas barrier capability and stable gas barrier performance, and the interlayer stripping force and the barrier performance can not be obviously deteriorated after the coating is subjected to continuous mechanical deformation, pressure cooking and other external actions.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to an aqueous coating liquid, a preparation method thereof and a gas barrier film.
Background
Foods, medicines, electronic products, and the like are easily deteriorated by the action of gases such as water vapor and oxygen, and in order to maintain their performance and function, they need to be packaged with a material having a sufficient gas barrier ability. Gas barrier materials that are currently more commonly used include: polyvinylidene chloride films, multilayer co-extruded ethylene vinyl alcohol copolymers (EVOH), metal foils or plastic films with deposited metal layers, vapor-deposited or reaction-plated oxide type films, and the like.
Polyvinylidene chloride films have excellent barrier properties and are not sensitive to moisture, but are sensitive to temperature and generate dioxin with very high toxicity after incineration, and are gradually replaced by other barrier materials; the deterioration of the gas barrier performance of the multilayer co-extrusion EVOH is very serious along with the increase of humidity, so the application field of the multilayer co-extrusion EVOH is also greatly limited; although the barrier performance of the metal foil or the plastic film deposited with the metal layer and the gas barrier performance under high temperature and high humidity are excellent, the problems that the content is invisible, the microwave heating is not available, the waste after use is difficult to treat and the like exist; the vapor-deposited or reaction-plated oxide thin film has the advantages of transparency, no pollution, insignificant variation of gas barrier properties with temperature and humidity, capability of microwave heating and the like, but has serious deterioration of barrier properties after vacuum-pumping, pressure cooking and other treatments, and has a risk of reducing interlayer adhesion properties. As can be seen, the existing gas barrier material films still remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Accordingly, an object of the present invention is to provide an aqueous coating liquid, a method for producing the same, and a gas barrier film. The aqueous coating liquid has the advantages of good stability, strong coatability and environmental friendliness, and the formed coating has excellent gas barrier capability and stable gas barrier performance, and the interlayer stripping force and the barrier performance can not be obviously deteriorated after the coating is subjected to continuous mechanical deformation, pressure cooking and other external actions.
In one aspect of the present invention, an aqueous coating solution is provided. According to an embodiment of the present invention, the aqueous coating liquid includes: 100 parts of water-soluble polymer, 10-150 parts of siloxane hydrolysate and nano oxide, 0.1-20 parts of first cross-linking agent, 0.1-10 parts of second cross-linking agent and 1000-12000 parts of solvent, wherein the first cross-linking agent comprises covalent cross-linking agent, and the second cross-linking agent comprises dynamic cross-linking agent.
The aqueous coating liquid of the above embodiment of the present invention has at least the following advantageous effects: 1) The covalent crosslinking network ensures that the coating has certain mechanical strength and the capabilities of resisting water boiling and pressure boiling, can resist mechanical deformation and the swelling action of water in the pressure boiling process, has certain dynamic performance, and can break dynamic bonds under external actions (such as mechanical deformation, damp-heat impact, pressure boiling and the like), and re-form the corresponding crosslinking network after the external actions are removed, so that most of stress can be buffered in the process, further the damage of the external action force to the inside of the coating is reduced, and the gas barrier film with the coating can not obviously deteriorate in the lower-layer adhesion and gas barrier performance under the external actions (such as kneading, vacuumizing, water boiling, pressure boiling and the like); 2) By introducing the siloxane hydrolysate and the nano oxide with the above dosage, on one hand, a network structure which is bonded and penetrated through chemical bonds can be formed between the water-soluble polymer and the siloxane hydrolysate, the water resistance and the stability of a coating formed by the coating liquid under the conditions of high temperature and high humidity are improved, on the other hand, the nano oxide can be filled in gaps of the network structure, the coating liquid is ensured to have lower volume shrinkage rate in the film forming process, and meanwhile, the formed coating has excellent gas barrier performance; 3) The aqueous coating liquid has the advantages of good stability, strong coatability and environmental friendliness, and the formed coating has excellent gas barrier capability and stable gas barrier performance, and the interlayer stripping force and the barrier performance between the coating and a substrate layer are not obviously deteriorated after the coating is subjected to external actions such as large (continuous) mechanical deformation (such as kneading), vacuum pumping, water boiling, pressure cooking and the like.
In addition, the aqueous coating liquid according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the weight ratio of the siloxane hydrolysate to the nano-oxide, based on the amount of silica in the siloxane hydrolysate, is from 1: (2 to 50).
In some embodiments of the invention, the weight ratio of the first crosslinking agent to the second crosslinking agent is (1 to 10): 1.
in some embodiments of the present invention, the aqueous coating solution further comprises: 0.01-10 parts of auxiliary agent, wherein the auxiliary agent comprises at least one selected from wetting agent, coupling agent, adhesion promoter and flatting agent.
In some embodiments of the invention, the water soluble polymer comprises hydrophilic functional groups comprising hydroxyl groups.
In some embodiments of the invention, the water soluble polymer comprises at least one selected from polyvinyl alcohol, starch, cellulose, chitosan, polyacrylic acid, polymaleic anhydride, or modified polymers of the foregoing polymers.
In some embodiments of the invention, the siloxane hydrolysate comprises Si (OR) 4 Hydrolyzing under acidic condition to obtain product, wherein R is C 1-8 An alkyl group.
In some embodiments of the present invention, the nano-oxide comprises at least one selected from the group consisting of alumina, silica, zinc oxide, titania, zirconia, magnesium carbonate, calcium carbonate, barium sulfate.
In some embodiments of the invention, the nano-oxide has an average particle size of 1 to 100nm.
In some embodiments of the invention, the nano-oxide is a nanoparticle that has been surface modified with a coupling agent.
In some embodiments of the present invention, the first crosslinking agent comprises at least one selected from aldehydes, acids, anhydrides, amino resins, isocyanates, silane coupling agents.
In some embodiments of the invention, the second crosslinking agent comprises boric acid and a metal salt.
In some embodiments of the invention, the solvent comprises water and/or an alcohol.
In some embodiments of the present invention, the hydrophilic functional groups of the water-soluble polymer comprise not less than 80 mole percent of the hydroxyl groups.
In some embodiments of the invention, the siloxane hydrolyzate is Si (OR) 4 Hydrolyzing the obtained product under acidic condition with pH value not more than 4.
In some embodiments of the invention, the nano-oxide has an average particle size of 3 to 50nm.
In some embodiments of the present invention, the nano-oxide is a nano-oxide whose surface has a hydroxyl content of 1 to 100mmol/nm after surface modification by a coupling agent 2 。
In some embodiments of the invention, the weight ratio of the boric acid to the metal salt is (1 to 30): 1.
in some embodiments of the invention, the metal salt comprises at least one selected from the group consisting of zinc chloride, zinc acetate, ferric chloride, calcium chloride, cupric chloride, ferric oxide, sodium chloride.
In some embodiments of the invention, the second crosslinker further comprises a chelating ligand, the molar ratio of the chelating ligand to the metal salt is (1-4): 1.
in some embodiments of the present invention, the volume ratio of the water to the alcohol in the solvent is (50 to 1): (1-10).
In some embodiments of the present invention, the hydrophilic functional groups of the water-soluble polymer have a hydroxyl group content of not less than 85 mole%.
In some embodiments of the invention, the chelating ligand comprises at least one selected from the group consisting of ethylenediaminetetraacetic acid, acetylacetone, and ethyl acetoacetate.
In some embodiments of the present invention, the volume ratio of the water to the alcohol in the solvent is (20 to 1): (1-5).
In still another aspect of the present invention, the present invention provides a method for preparing the above-mentioned aqueous coating liquid. According to an embodiment of the invention, the method comprises: (1) Mixing a water-soluble polymer, a siloxane hydrolysate, a nano oxide and a solvent according to a predetermined ratio to obtain a mixed solution; (2) Mixing the mixed solution with a first crosslinking agent and a second crosslinking agent. Compared with the prior art, the method has the advantages of simple process, easy operation, suitability for industrial production, good stability, strong coatability and environmental friendliness of the aqueous coating liquid, the formed coating has excellent gas barrier capability, the gas barrier property is stable, and the interlayer stripping force and the barrier property between the coating and the substrate layer can not be obviously deteriorated after the coating is subjected to external actions such as large (continuous) mechanical deformation (such as kneading), vacuum pumping, water boiling, pressure cooking and the like.
In addition, the method for preparing an aqueous coating solution according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, in step (1): dissolving the water-soluble polymer prior to said mixing; and/or, the mixing further comprises: adding the auxiliary agent in a preset ratio.
In yet another aspect of the invention, a gas barrier film is provided. According to an embodiment of the present invention, the gas barrier film includes a base film layer and a barrier layer provided on at least one surface of the base film layer, the barrier layer being formed using the above-described aqueous coating liquid or the aqueous coating liquid obtained using the above-described method for preparing an aqueous coating liquid. The features and effects described for the above-mentioned aqueous coating liquid and the method of preparing the aqueous coating liquid are also applicable to the gas barrier film, and are not described herein again. In general, compared with the prior art, the gas barrier film not only has excellent initial gas barrier performance, but also can ensure that the interlayer adhesion performance and the gas barrier performance are not obviously deteriorated after external actions such as kneading, vacuumizing, boiling in water, pressure cooking and the like, and the gas barrier performance is stable.
In addition, the gas barrier film according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the thickness of the base film layer is 5 to 300 μm.
In some embodiments of the invention, the barrier layer has a thickness of 0.05 to 5 μm.
In some embodiments of the present invention, the base film layer comprises at least one selected from the group consisting of a polyolefin film, a polyester film, and a polyamide film.
In some embodiments of the present invention, the base film layer further comprises: the bottom layer, the bottom is established on at least one surface of base membrane layer, the barrier layer is established the bottom is kept away from on at least some surface of one side of base membrane layer.
In some embodiments of the invention, the gas barrier film further comprises: an inorganic material layer disposed on at least one surface of the base film layer, the barrier layer being disposed on at least a portion of a surface of a side of the base film layer remote from the inorganic material layer.
In some embodiments of the present invention, the base layer is a bulk layer formed by activating a surface of the base film, or the base layer is a resin layer formed on a surface of the base film.
In some embodiments of the present invention, the resin layer includes at least one selected from the group consisting of a polyester resin, a polyurethane resin, an acrylic resin, a styrene resin, and an amino resin.
In some embodiments of the invention, the underlayer has a thickness of 0.005 to 5 μm.
In some embodiments of the invention, the inorganic material layer comprises at least one selected from the group consisting of alumina, silica, iron oxide, zirconia, and silicon nitride.
In some embodiments of the present invention, the thickness of the inorganic material layer is 5 to 500nm.
In some embodiments of the present invention, the inorganic material layer includes a plurality of sub-inorganic material layers, the barrier layer includes a plurality of sub-barrier layers, the plurality of sub-inorganic material layers and the plurality of sub-barrier layers are alternately arranged in a direction away from the base film layer, and an outermost layer of the gas barrier film is the sub-barrier layer.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic view of the structure of a gas barrier film according to one embodiment of the present invention;
fig. 2 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention;
fig. 3 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention;
fig. 4 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention;
fig. 5 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention;
fig. 6 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention;
fig. 7 is a schematic view of the structure of a gas barrier film according to still another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In one aspect of the present invention, an aqueous coating solution is provided. According to an embodiment of the present invention, the aqueous coating liquid includes: 100 parts of water-soluble polymer, 10-150 parts of siloxane hydrolysate and nano oxide, 0.1-20 parts of first cross-linking agent, 0.1-10 parts of second cross-linking agent and 1000-12000 parts of solvent, wherein the first cross-linking agent comprises covalent cross-linking agent, and the second cross-linking agent comprises dynamic cross-linking agent. In the coating liquid, the covalent cross-linking agent is mainly used for improving the mechanical strength of the coating, so that the coating can resist the mechanical deformation and the swelling effect of water in the pressurizing and cooking process; the dynamic cross-linking agent is mainly used for preventing the interlayer adhesion and the gas barrier performance of the coating from being obviously deteriorated after the coating is subjected to external actions such as large mechanical deformation, pressure cooking and the like, and optionally, the first cross-linking agent can be completely a covalent cross-linking agent, and the second cross-linking agent can be completely a dynamic cross-linking agent.
The aqueous coating liquid of the above embodiment of the present invention has at least the following advantageous effects: 1) By adding the covalent crosslinking agent and the dynamic crosslinking agent, at least two crosslinking forms can exist in a coating formed by the coating liquid, wherein the covalent crosslinking network ensures that the coating has certain mechanical strength and capabilities of resisting boiling and pressure boiling, can resist mechanical deformation and swelling action of water in the pressure boiling process, has certain dynamic performance, breaks a dynamic bond under external action (such as mechanical deformation, damp and hot impact, pressure boiling and the like), and can re-form a corresponding crosslinking network after the external action is removed, so that most of stress can be buffered in the process, further, the damage of the external action force to the inside of the coating is reduced, and the condition that the adhesion and the gas barrier performance of a gas barrier film with the coating cannot be obviously degraded under the external action (such as rubbing, vacuumizing, boiling, pressure boiling and the like) is ensured; 2) By introducing the siloxane hydrolysate and the nano oxide with the above dosage, on one hand, a network structure which is bonded and penetrated through by chemical bonds can be formed between the water-soluble polymer and the siloxane hydrolysate, the water resistance and the stability of a coating formed by the coating liquid under the conditions of high temperature and high humidity are improved, on the other hand, the nano oxide can be filled in gaps of the network structure, the coating liquid is ensured to have lower volume shrinkage rate in the film forming process, and meanwhile, the formed coating has excellent gas barrier performance; 3) The aqueous coating liquid has the advantages of good stability, strong coatability and environmental friendliness, and the formed coating has excellent gas barrier capability and stable gas barrier performance, and the interlayer stripping force and the barrier performance between the coating and a substrate layer are not obviously deteriorated after the coating is subjected to external actions such as large (continuous) mechanical deformation (such as kneading), vacuum pumping, water boiling, pressure cooking and the like.
The aqueous coating liquid of the above-described embodiment of the present invention will be described in detail below.
At present, coating liquids for forming gas barrier layers include water-soluble polymers having hydroxyl groups and siloxanes or siloxane hydrolysates, but in order to make the coating layer capable of withstanding boiling or steaming without swelling, the amount of inorganic silicon oxides must be increased, and the increase in the proportion thereof causes the coating layer to be harder, and the coating layer is very likely to fail under mechanical deformation impact (especially rubbing test, vacuum pumping, etc.), thereby causing a decrease in interlayer adhesion and barrier properties; in addition, there is also a scheme of a gas barrier coating liquid including a copolymer, an unsaturated nitrile, an unsaturated compound monomer having a hydroxyl group, an isocyanate-based curing agent, and the like, but a gas barrier layer formed by the coating liquid is poor in compactness, has a limited improvement in barrier ability to an inorganic barrier layer, is an organic solvent system, and has a large environmental pressure; further, there is a proposal of forming a gas barrier layer on an inorganic thin film by using a polyester resin, but in this proposal, the interlayer peeling force of the gas barrier film layer is remarkably reduced after high-pressure cooking; further, there is a method of forming a gas barrier layer with a polyvinyl alcohol crosslinking agent (without a dynamic crosslinking agent), but the gas barrier layer has a limited oxygen barrier ability and is difficult to withstand large mechanical deformation and impact of boiling or retort. By adopting the technical scheme of the embodiment of the invention, the water-soluble polymer, the siloxane hydrolysate, the nano oxide, the covalent crosslinking agent, the dynamic crosslinking agent and the solvent are mixed according to the predetermined proportion, so that the problems can be effectively solved or improved, the formed gas barrier layer has excellent gas barrier capability and stable gas barrier performance, and the interlayer peeling force and barrier performance can not be obviously deteriorated after the gas barrier layer is subjected to external actions such as continuous mechanical deformation, pressure cooking and the like, thereby not only protecting the peer flexible barrier layer and improving the performance of the peer flexible barrier layer in resisting mechanical deformation, water cooking or pressure cooking, but also protecting other brittle barrier layers such as an oxide layer with barrier performance obtained by a coating mode and the like.
According to the embodiment of the present invention, in the aqueous coating liquid, the weight part of the first crosslinking agent is 0.1 to 20, for example, may be 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 18, 20, etc.; the weight portion of the second cross-linking agent is 0.2 to 10, for example, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc., wherein the first cross-linking agent can be a covalent cross-linking agent and the second cross-linking agent can be a dynamic cross-linking agent. The inventors have found that if the amount of the first crosslinking agent is too small, the degree of crosslinking of the water-soluble polymer is insufficient, and the resistance of the coating layer formed is poor, and that if the amount of the first crosslinking agent is too large, the coating layer formed from the coating liquid is hard, hardly undergoes large mechanical impact deformation, and has poor oxygen barrier properties; if the amount of the second crosslinking agent is too small, the dynamic crosslinking component in the formed barrier coating is insufficient, and the barrier coating hardly acts to release stress, and further, the interlayer adhesion and the gas barrier property of the gas barrier film material having the coating are greatly reduced after being subjected to large mechanical deformation or boiling with water or high-pressure cooking, and if the amount of the second crosslinking agent is too large, the boiling resistance or pressure cooking resistance of the formed coating is not good, and the stability of the coating liquid is affected. In the present invention, by controlling the amounts of the first crosslinking agent and the second crosslinking agent within the above ranges, it is possible to ensure not only that the coating formed from the coating liquid has excellent resistance to boiling and retort under pressure, but also that the gas barrier film having the coating layer does not undergo significant deterioration in interlayer adhesion and gas barrier properties after being subjected to extreme conditions such as large mechanical deformation or retort under pressure.
According to an embodiment of the present invention, the weight ratio of the first crosslinking agent and the second crosslinking agent may be (1 to 10): 1, for example, may be 1: 1. 2: 1. 3: 1. 4: 1.5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10:1, etc. The inventors have found that if the weight ratio of the first crosslinking agent to the second crosslinking agent is too small, the boiling resistance or retort resistance of the coating is liable to be poor; if the weight ratio of the first crosslinking agent to the second crosslinking agent is too large, the dynamic crosslinking component in the coating layer tends to be insufficient, and it is difficult to exert a stress-releasing action, and the interlayer adhesiveness and the gas barrier property of a gas barrier film (which may include a base film layer and a gas barrier coating layer, for example) formed using the coating liquid are deteriorated after being subjected to large mechanical deformation and boiling with water and pressure cooking. In the present invention, by controlling the weight ratio of the first crosslinking agent to the second crosslinking agent within the above range, it is more advantageous that the gas barrier film formed by using the coating liquid has excellent boiling and pressure retort resistance and has a stable gas barrier property after an external action.
According to an embodiment of the present invention, the weight ratio of the siloxane hydrolysate to the nano-oxide may be 1: (2 to 50), for example, 1.0, 1.4.0, 1. The inventors found that if the weight ratio of the siloxane hydrolyzate to the nano oxide is too low, insufficient strength of action between the organic and inorganic components is likely to result, and the coating layer formed from the aqueous coating liquid has poor resistance to high-temperature steaming; if the weight ratio of the siloxane hydrolysate to the nano oxide is too high, the problem of large volume shrinkage rate exists during coating curing, and the smoothness and the barrier property of the film material are influenced. According to the invention, the weight ratio of the siloxane hydrolysate to the nano oxide is controlled within the range, so that the high-temperature cooking resistance of the coating can be improved while the curing performance of the coating liquid is ensured to be stable.
According to embodiments of the present invention, the water-soluble polymer employed in the present invention may include hydrophilic functional groups, which may include, but are not limited to, hydroxyl groups, for example, the hydrophilic functional groups may also include carboxyl groups, amino groups, ether linkages, etc., wherein the introduction of non-hydroxyl hydrophilic functional groups may introduce various crosslinking sites in the polymer, improving the overall performance of the final coating. Further, the mole percentage content of hydroxyl functional groups in all hydrophilic functional groups of the water-soluble polymer can be not less than 80%, and the inventor finds that if the content of the hydroxyl functional groups is too low, dense accumulation is difficult to form between polymer chain segments, which easily causes the oxygen blocking capability of the coating to be limited; preferably, the molar percentage content of the hydroxyl functional group among all the hydrophilic functional groups of the water-soluble polymer may be not less than 85%, whereby the denseness of the coating layer may be further improved, and the gas barrier ability and effect of the coating layer may be improved. In addition, it should be noted that the kind and composition of the water-soluble polymer in the present invention are not particularly limited, and those skilled in the art can flexibly select the water-soluble polymer according to the actual situation, for example, the water-soluble polymer may include one polymer or a plurality of polymers, the mole percentage content of the hydroxyl functional groups in one or more polymers in all hydrophilic functional groups is not less than 80%, preferably not less than 85%, and the rest of the non-hydroxyl hydrophilic groups can be obtained by modifying the same polymer or by introducing a polymer containing other hydrophilic functional groups. Such as: polyvinyl alcohol is used as the water-soluble polymer, and the hydroxyl groups thereon account for 90% of all hydrophilic functional groups, and the remaining 10% may be carboxyl groups, which may be introduced in polyvinyl alcohol, or may be obtained by introducing a calculated amount of polyacrylic acid. For another example, the water-soluble polymer may include at least one selected from polyvinyl alcohol, starch, cellulose, chitosan, polyacrylic acid, polymaleic anhydride, and/or at least one of the above polymers modified with polymaleic anhydride. Preferably, the water soluble polymer may be polyvinyl alcohol (PVA), such as may be selected from Leliso KL318, KL118, 117, 2117, R-3109, R-2105, wacker P-6060, and the like.
According to embodiments of the present invention, the siloxane hydrolyzate may include Si (OR) 4 (alkoxysilane) hydrolysis to give a product, wherein R may be C 1-8 Alkyl, more preferably, R may be C 1-4 The alkyl group may be, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or the like. According to a specific example of the invention, si (OR) 4 May include a compound selected from tetramethoxysilane Si (OCH) 3 ) 4 Tetraethoxysilane Si (OC) 2 H 5 ) 4 Tetrapropoxysilane Si (OC) 3 H 7 ) 4 Tetra-butoxysilane Si (OC) 4 H 9 ) 4 And the like. Further, the above Si (OR) 4 A series of hydrolytic condensation reactions can be carried out under the catalysis of acid OR alkali, and Si (OR) can be selected to improve the intersolubility of the hydrolytic condensation reaction product with a water-soluble polymer 4 The hydrolysis is carried out under acidic conditions at a pH of not more than 4, whereby the stability of the hydrolysate can be further improved, and the inventors have found that if the pH of the hydrolysis environment is more than 4, the stability of the hydrolysate may be reduced. The method for adjusting the pH of the system is not particularly limited, and may be, for example, a method of adjusting the pH by adding an acid solution, and the type of the acid used is not particularly limited, and may be, for example, sulfuric acid, hydrochloric acid, or nitric acidInorganic acids such as acids, and/or organic acids such as acetic acid and tartaric acid. According to a specific example of the present invention, si (OR) 4 In the process of forming a uniform system through hydrolytic condensation reaction under the catalysis of acid, the pH value of the reaction system can be maintained to be not more than 4, the temperature is 2-50 ℃, and preferably 5-40 ℃, so that the particle size of a hydrolysate can be controlled within 100nm, and the oxygen barrier performance of a coating formed by the aqueous coating liquid can be improved.
According to the embodiment of the present invention, the kind of the nano-oxide in the present invention is not particularly limited, and those skilled in the art can flexibly select the nano-oxide according to the actual situation, and for example, at least one selected from alumina, silica, zinc oxide, titanium oxide, zirconia, magnesium carbonate, calcium carbonate, and barium sulfate may be included. The average particle size of the nano-oxide may be 1 to 100nm, for example, 1nm, 3nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc. the inventors found that if the particle size of the nano-oxide is too small, the preparation and storage are difficult; if the particle size of the nano oxide is too large, the barrier property of a coating formed by the aqueous coating liquid can be influenced, and the barrier property of the coating formed by the coating liquid can be improved on the basis of simplifying the processing and storing difficulties by controlling the average particle size of the nano oxide within the range. Further, the average particle size of the nano oxide may preferably be 3 to 50nm, whereby the barrier property of the coating layer may be further improved.
According to the embodiment of the present invention, the nano-oxide may be nano-oxide particles surface-modified by a coupling agent, and it should be noted that the kind of the coupling agent used for modification is not particularly limited, and those skilled in the art can flexibly select the coupling agent according to the actual situation, for example, at least one of a silane coupling agent, a titanate coupling agent, or a phosphoric acid coupling agent can be selected to modify the surface of the nano-oxide so that the hydroxyl content on the surface is 1 to 100mmol/nm 2 Thereby, a better dispersion property can be obtained. The inventor finds that if the hydroxyl content on the surface of the nano oxide is too low, the oxygen resistance of a coating formed by the aqueous coating liquid is not improved; if the hydroxyl on the surface of the nano oxideToo high a radical content in turn affects the resistance of the coating formed from the aqueous coating solution to high temperatures and humidity.
According to an embodiment of the present invention, the first crosslinking agent in the present invention may be a covalent crosslinking agent, for example, a small molecule crosslinking agent or a polymer crosslinking agent, and specifically may include at least one selected from aldehydes, acids, acid anhydrides, amino resins, isocyanates, and silane coupling agents, and by adding the above crosslinking agent, a covalent crosslinking network may be formed in the coating layer, so that the coating layer has a certain mechanical strength and can resist mechanical deformation and swelling action of moisture during autoclaving; the second crosslinking agent can be a dynamic crosslinking agent, for example, boric acid and metal salt can be included, and a dynamic crosslinking network can be formed in the coating by adding the second crosslinking agent, so that the crosslinking network is broken under the external action alternatively, and corresponding acting force can be formed when the external action is removed, and the interlayer adhesion and the gas barrier performance of the coating and the gas barrier film formed by the aqueous coating liquid can not be obviously deteriorated after the coating and the gas barrier film are subjected to large mechanical deformation and pressure cooking. It should be noted that the kind of the metal salt in the present invention is not particularly limited, and those skilled in the art can flexibly select the metal salt according to the actual situation, for example, the metal salt may include at least one selected from zinc chloride, zinc acetate, ferric chloride, calcium chloride, copper chloride, ferric oxide, and sodium chloride, and the metal salt may perform a coordination crosslinking reaction with a hydrophilic group (such as hydroxyl group, amino group, or carboxyl group, etc.) in the water-soluble polymer, so as to improve the compactness of the coating layer, and the coordination bond has a certain degree of reversibility and may also act as a stress releasing function, thereby improving the interlayer adhesion and gas barrier property of the coating layer with the substrate layer under the external action.
According to an embodiment of the present invention, in the second crosslinking agent, the weight ratio of boric acid and the metal salt may be (1 to 30): 1, for example, 1, 2, 1, 3, 1, 4, 1, 5; if the boric acid content is too high, the gelation time of the coating liquid is obviously shortened, and the use performance of the coating liquid is affected.
According to an embodiment of the present invention, the second crosslinking agent may further include a chelating ligand, wherein the chelating ligand may include at least one selected from the group consisting of ethylenediaminetetraacetic acid, acetylacetone, and ethyl acetoacetate. Further, the molar ratio of the chelating ligand to the metal salt may be (1 to 4): 1, for example, 1, 1.5; if the chelating ligand proportion is too high, the cost is increased. In the present invention, by controlling the amount of the chelating ligand within the above range, the coatability and production cost of the coating solution can be better considered.
According to an embodiment of the present invention, the solvent may be used in an amount of 1000 to 12000 parts by weight, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, and the like, in the aqueous coating solution. Further, the solvent used for the aqueous coating solution may include water and/or alcohol, and may be, for example, a mixed solution of water and alcohol. The alcohol may be a water-miscible monohydric alcohol, and may include at least one selected from methanol, ethanol, isopropanol, and n-propanol, for example. According to some embodiments of the present invention, the volume ratio of water to alcohol in the solvent may be (50 to 1): (1 to 10), for example, the ratio of 20: 1. 10: 1. 1:1 or 10:1, etc., the inventors have found that if the content of the alcohol in the solvent is too low, the wettability of the aqueous coating liquid may be deteriorated and the effective dispersion of the auxiliary may be affected; if the content of the alcohol in the solvent is too high, the safety of the production process may be affected, and the production cost may be increased. Preferably, the volume ratio of water to alcohol in the solvent may be (20 to 1): (1 to 5), whereby the coating properties of the coating liquid, the production cost and the production safety can be more satisfactorily satisfied.
According to the embodiment of the present invention, the aqueous coating solution may further include 0.01 to 10 parts by weight of an auxiliary agent, for example, the parts by weight of the auxiliary agent may be 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the like. It should be noted that the specific kind of the auxiliary agent in the present invention is not particularly limited, and those skilled in the art can flexibly select the auxiliary agent according to the actual situation, and for example, at least one selected from a wetting agent, a coupling agent, an adhesion promoter, and a leveling agent may be included, and by adding the auxiliary agent, better coating effect, appearance, and the like may be obtained.
In still another aspect of the present invention, the present invention provides a method for preparing the above-mentioned aqueous coating liquid. According to an embodiment of the invention, the method comprises: (1) Mixing a water-soluble polymer, a siloxane hydrolysate, a nano oxide and a solvent according to a predetermined ratio to obtain a mixed solution; (2) The mixed solution is mixed with a first crosslinking agent and a second crosslinking agent. Compared with the prior art, the method has the advantages of simple process, easy operation, suitability for industrial production, good stability, strong coatability and environmental friendliness of the aqueous coating liquid, the formed coating has excellent gas barrier capability, the gas barrier property is stable, and the interlayer stripping force and the barrier property between the coating and the substrate layer can not be obviously deteriorated after the coating is subjected to external actions such as large (continuous) mechanical deformation (such as kneading), vacuum pumping, water boiling, pressure cooking and the like.
According to the embodiment of the present invention, in the step (1), the siloxane hydrolysate may be provided by hydrolyzing an alkoxysilane compound, for example, the alkoxysilane compound may be hydrolyzed under acidic conditions and mixed with the aqueous polymer, the nano-oxide and the solvent at a predetermined ratio during or after completion of the hydrolysis, or the alkoxysilane compound may be hydrolyzed in a mixed solution system after the alkoxysilane compound, the aqueous polymer, the nano-oxide and the solvent are mixed at a predetermined ratio. In addition, before the mixing, the aqueous polymer may be dissolved in a part or all of the solvent in advance, and the obtained solution may be mixed with the remaining components, thereby further facilitating the sufficient mixing of the components.
According to an embodiment of the present invention, in step (1), the mixing may further include: the addition of the auxiliary agent in a predetermined ratio, for example, may be further added during or after the mixing of the water-soluble polymer, the siloxane hydrolyzate, the nano-oxide, the solvent, and preferably, after the hydrolysis of the alkoxysilane compound is added and the addition of the water-soluble polymer and the nano-oxide is completed, the addition of the auxiliary agent in a predetermined ratio may be further added to further improve the coating properties of the coating liquid, the appearance of the coating layer, the gas barrier properties, and the like.
It should be noted that all the features and effects described for the above aqueous coating liquid are also applicable to the method for preparing the aqueous coating liquid, and are not described in detail herein.
In yet another aspect of the invention, a gas barrier film is provided. According to an embodiment of the present invention, as will be understood with reference to fig. 1 to 2, the gas barrier film includes a base film layer 10 and a barrier layer 20, the barrier layer 20 being provided on at least one surface of the base film layer 10, the barrier layer 20 being formed using the above-described aqueous coating solution or an aqueous coating solution obtained using the above-described method for preparing an aqueous coating solution. It is to be noted that the features and effects described for the above-mentioned aqueous coating liquid and the method for preparing the aqueous coating liquid are also applicable to the gas barrier film, and will not be described herein again. In general, the gas barrier film is excellent in initial gas barrier properties, and can ensure stable gas barrier properties without significant deterioration in interlayer adhesion properties and gas barrier properties after external actions such as kneading, vacuuming, poaching, pressure cooking, and the like.
According to the embodiment of the present invention, the specific kind of the base film layer 10 in the gas barrier film is not particularly limited, and those skilled in the art can flexibly select according to actual needs, and for example, may include at least one selected from polyolefin-based films, polyester-based films, and polyamide-based films, and further for example, the base film layer 10 may be selected from 1) transparent resin films, amorphous polyolefin-based films including polyolefins, cyclic polyolefins, etc. of monomer polymers or copolymers of ethylene, propylene, butene, etc.; 2) Polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate; 3) Polyamide-based films such as nylon 6, nylon 66, and nylon 12; 4) EVOH, polyvinyl butyral, fluorine resins, biodegradable resins, and the like, which are partial hydrolyzates of ethylene-vinyl acetate copolymers. The thickness of the base film layer may be 5 to 300. Mu.m, preferably 5 to 150. Mu.m.
According to an embodiment of the present invention, the thickness of the barrier layer 20 may be 0.05 to 5 μm, for example, 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or the like. The inventors have found that if the thickness of the barrier layer is too small, it is difficult to exert an effective barrier effect; if the thickness of the barrier layer is too large, the coating may crack, which affects the barrier performance and the interlayer adhesion. In the present invention, by limiting the thickness of the barrier layer to the above range, the barrier properties and the stress accumulation of the barrier layer can be maintained at a preferable level. In addition, it should be noted that the barrier layer 20 may be disposed on one surface of the base film layer 10 (as understood in conjunction with fig. 1) or on two surfaces disposed opposite to each other (as understood in conjunction with fig. 2) according to different usage requirements.
According to an embodiment of the present invention, as understood in conjunction with fig. 3-4, the base film layer 10 may further include: the bottom layer 11, the bottom layer 11 may be disposed on at least one surface of the base film layer 10, and the barrier layer 20 may be disposed on at least a portion of a surface of the bottom layer 11 away from the base film layer 10, wherein the bottom layer may be utilized to effectively shield the surface defects of the base film layer, thereby improving the surface flatness of the base film layer. In the present invention, the primer layer 11 may be a bulk layer obtained by activating the surface of the base film layer 10, or may be a resin layer formed on the surface of the base film layer 10, wherein the activating method and the selection of the resin are not particularly limited, and may be selected by those skilled in the art according to the actual needs, for example, the activating treatment may be obtained by performing corona and/or plasma treatment on the base film layer, and the resin layer may be formed by selecting at least one of a solvent-based or water-soluble polyester resin, a polyurethane resin, an acrylic resin, a styrene resin, and an amino resin. According to some embodiments of the present invention, the thickness of the base layer 11 may be 0.005 to 5 μm, and preferably may be 0.01 to 1 μm, and the inventors have found that, if the thickness of the base layer is too small, it is difficult to effectively shield the defects on the surface of the base film layer; if the bottom layer is too thick, the planarization function of the base film layer cannot be increased, but the cost is increased and the risk of cracking exists. In addition, it should be noted that the bottom layer 11 may be formed on one surface of the base film layer 10 (as understood in conjunction with fig. 3) or on two surfaces disposed oppositely (as understood in conjunction with fig. 4).
According to an embodiment of the present invention, as understood in conjunction with fig. 5 to 6, the gas barrier film may further include: an inorganic material layer 30, the inorganic material layer 30 may be disposed on at least one surface of the base film layer 10, and in this case, the barrier layer 20 may be disposed on at least a portion of a surface of the inorganic material layer 30 on a side away from the base film layer 10. When the base film layer 10 further includes the base layer 11, the inorganic material layer 30 may be disposed on the base layer 11, and the inorganic material layer 30 may be disposed on at least a part of a surface of the base layer 11 on a side away from the base film layer 10. In addition, the material and formation method of the inorganic material layer in the present invention are not particularly limited, and those skilled in the art can flexibly select the material and formation method according to actual needs, for example, the inorganic material layer may include at least one selected from alumina, silicon oxide, iron oxide, zirconium oxide, and silicon nitride, the inorganic material layer may be formed by a method such as evaporation, sputtering, or PECVD, and the water and oxygen barrier performance of the film material may be further improved by providing the inorganic material layer. The inorganic material layer 30 may have a thickness of 5 to 500nm, for example, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, etc., and the inventors have found that if the thickness of the inorganic material layer is too small, the gas barrier performance may not satisfy the use requirement; if the thickness of the inorganic material layer is too large, cracking may occur, and the barrier performance may be degraded in the subsequent use process. Preferably, the thickness of the inorganic material layer 30 may be 10 to 50nm, so that the risk of cracking thereof may be reduced on the basis of satisfying the barrier properties, and the use stability of the gas barrier film may be ensured.
According to an embodiment of the present invention, as understood in connection with fig. 7, the inorganic material layer 30 may include a plurality of sub-inorganic material layers 31, the barrier layer 20 may include a plurality of sub-barrier layers 21, the plurality of sub-inorganic material layers 31 and the plurality of sub-barrier layers 21 may be alternately arranged in a direction away from the base film layer 10, and an outermost layer of the gas barrier film is the sub-barrier layer 21. When such a structural design is employed, the thickness of each sub inorganic material layer 31 may preferably be 10 to 100nm, and the thickness of each sub barrier layer 31 may preferably be 0.005 to 5 μm. In addition, it should be noted that the number of the sub-barrier layers and the sub-inorganic material layers in the actual gas barrier film product is not limited by fig. 7.
In addition, the coating method of forming the barrier layer by using the aqueous coating liquid in the present invention is not particularly limited, and those skilled in the art can flexibly select the coating method according to actual conditions, and for example, one or more of roll coating, gravure coating, blade coating, slot coating, extrusion coating, air knife coating, dip coating, spray coating, and the like can be used.
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
General materials and methods for the examples and comparative examples:
(1) Preparation of water-soluble polymer solution:
p1: 50g of PVA 117 (Coly) was added to 950g of water, the temperature was raised to 95 ℃ and the temperature was maintained for 5h, and the whole process was stirred to give a solution with a solids content of 5%, denoted as P1.
P2: 50g PVA KL318 (Coly) was added to 950g water, heated to 95 deg.C, and the mixture was stirred for 5h to give a solution with 5% solids, denoted P2.
P3: 45g of PVA 117 (Coly) and 5g of ethylene maleic anhydride homopolymer E60 were added to 950g of water, the temperature was raised to 95 ℃, the temperature was maintained for 5 hours, and the whole process was stirred to obtain a solution with a solid content of 5%, which was designated as P3.
(2) Preparation of siloxane hydrolysate and nano-oxide dispersion:
s1: 28.8g of Tetraethoxysilane (TEOS), 8g of methanol, 56g of 0.1mol/L hydrochloric acid aqueous solution and 55.7g of nano-silica dispersion (silica content 30wt%, average particle diameter 3 nm) were mixed together and stirred at room temperature for 24 hours to obtain a hydrolysate, which was designated as S1.
S2: 1.2g TEOS, 8g methanol, 27g water, 56g 0.1mol/L hydrochloric acid aqueous solution, 55.7g nano silica dispersion (silica content 30wt%, average particle diameter 3 nm) were mixed together and stirred at room temperature for 24 hours to obtain a hydrolysate, which was designated as S2.
(3) Examples and comparative examples general procedure for forming gas barrier films:
depositing a 30nm thick silicon oxide layer on a 15 μm thick Polyamide (PA) film by chemical vapor deposition (PECVD) method to obtain a water permeability of 0.9 g.m -2 ·day -1 Oxygen permeability of 1.2cc m -2 ·day -1 . Coating liquid on the silicon oxide layer, curing at 120 deg.C for 1min to form a barrier layer coating, and drying to a thickness of 500nm to obtain the gas barrier film with the structure shown in FIG. 3.
Example 1
2000g of P1 liquid is taken, 58.8g of S1 liquid is added, and the mixture is stirred uniformly. 25g of 40% aqueous glyoxal solution was added and stirred until uniform, and the mixture was designated as T1. Dissolving 9.68g of boric acid, 0.32g of hexahydrate of ferric chloride and 0.46g of ethyl acetoacetate in 100g of water, and adding the dissolved solution into the rapidly stirred T1 solution to obtain a coating solution 1; the gas barrier film 1 was obtained by coating according to the general method for preparing a gas barrier film described above.
Example 2
2000g of P1 liquid was taken, 58.8g of S1 liquid was added, and the mixture was stirred uniformly. 50g of 40% aqueous glyoxal solution was added and stirred well and recorded as T2. Dissolving boric acid 1.94g, ferric chloride 0.06g and hexahydrate and ethyl acetoacetate 0.09g in water 100g, and adding the obtained solution into rapidly-stirred T2 solution to obtain coating solution 2; the gas barrier film 2 was obtained by coating using the general method for preparing a gas barrier film described above.
Example 3
2000g of P1 liquid was taken, 58.8g of S1 liquid was added, and the mixture was stirred uniformly. 50g of 40% aqueous glyoxal solution was added and stirred well and recorded as T3. Dissolving boric acid 1.0g, hexahydrate 1.0g, ferric chloride and ethyl acetoacetate 1.45g in water 100g, and adding the obtained solution to rapidly stirred T3 solution to obtain coating solution 3; the gas barrier film 3 was obtained by coating according to the general method for preparing a gas barrier film described above.
Example 4
2000g of P1 liquid was taken, 58.8g of S1 liquid was added, and the mixture was stirred uniformly. 50g of 40% aqueous glyoxal solution was added and stirred well and recorded as T4. Dissolving boric acid 1.94g, calcium chloride 0.06g and ethyl acetoacetate 0.09g in water 100g, and adding the dissolved solution into rapidly stirred T4 solution to obtain coating solution 4; the gas barrier film 4 was obtained by coating according to the general method for preparing a gas barrier film described above.
Example 5
2000g of P2 liquid was taken, 58.8g of S1 liquid was added, and the mixture was stirred uniformly. 50g of 40% aqueous glyoxal solution was added and stirred well and recorded as T5. Dissolving boric acid 1.94g, ferric chloride and hexahydrate 0.06g and ethyl acetoacetate 0.09g in water 100g, and adding the dissolved solution into rapidly stirred T5 solution to obtain coating solution 5; the gas barrier film 5 was obtained by coating according to the general method for preparing a gas barrier film described above.
Example 6
2000g of P3 liquid was added to 58.8g of S1 liquid, and the mixture was stirred uniformly. 50g of 40% aqueous glyoxal solution was added and stirred well and recorded as T6. Dissolving boric acid 1.94g, ferric chloride and hexahydrate 0.06g and ethyl acetoacetate 0.09g in water 100g, and adding the dissolved solution into rapidly stirred T6 solution to obtain coating solution 6; the gas barrier film 6 was obtained by coating using the general method for preparing a gas barrier film described above.
Example 7
2000g of P1 liquid is taken, 58.8g of S2 liquid is added, and the mixture is stirred uniformly. 50g of 40% aqueous glyoxal solution was added and stirred well and designated as T7. Dissolving boric acid 1.94g, ferric chloride and hexahydrate 0.06g and ethyl acetoacetate 0.09g in water 100g, and adding the dissolved solution into T7 solution under rapid stirring to obtain coating solution 7; the gas barrier film 7 was obtained by coating using the general method for preparing a gas barrier film described above.
Example 8
2000g of P1 liquid was added to 58.8g of S1 liquid, and the mixture was stirred uniformly. 20g of cyanamide resin 325 was added thereto and stirred uniformly, and the mixture was designated as T8. Dissolving boric acid 1.94g, ferric chloride 0.06g and hexahydrate, and ethyl acetoacetate 0.09g in water 100g, and adding the obtained solution into rapidly-stirred T8 solution to obtain coating solution 8; the gas barrier film 8 is obtained by coating using the general method for preparing a gas barrier film described above.
Comparative example 1
2000g of P1 liquid is taken, 58.8g of S2 liquid is added, and the mixture is stirred uniformly. Adding 50g of 40% glyoxal aqueous solution, and uniformly stirring to obtain a coating liquid 9; the gas barrier film 9 was obtained by coating according to the general method for preparing a gas barrier film described above.
Comparative example 2
2000g of P1 solution was added to 58.8g of S2 solution, and the mixture was stirred uniformly and denoted as T9. Dissolving boric acid 1.94g, ferric chloride and hexahydrate 0.06g and ethyl acetoacetate 0.09g in water 100g, and adding the dissolved solution into rapidly stirred T9 solution to obtain coating solution 10; the gas barrier film 10 is obtained by coating using the general method for preparing a gas barrier film described above.
Comparative example 3
2000g of P1 solution was added to 50g of 40% aqueous glyoxal solution, and the mixture was stirred uniformly and recorded as T10. Dissolving boric acid 1.94g, ferric chloride and hexahydrate 0.06g and ethyl acetoacetate 0.09g in water 100g, and adding the dissolved solution into rapidly stirred T10 solution to obtain coating solution 11; the gas barrier film 11 was obtained by coating using the general method for preparing a gas barrier film described above.
Comparative example 4
Depositing a 30nm thick silicon oxide layer on a 15 μm thick Polyamide (PA) film by chemical vapor deposition (PECVD) method to obtain a water permeability of 0.9 g.m -2 ·day -1 Oxygen permeability of 1.2cc m -2 ·day -1 To obtain the gas barrier film 12.
And (3) performance test and evaluation:
the gas barrier films obtained in examples 1 to 8 and comparative examples 1 to 4 were characterized under the same conditions by the following test methods, the characterization consisting of: the oxygen permeability and interlaminar peeling force of the composite membrane are obtained at the beginning of the gas barrier membrane and after kneading/cooking. The characterization results are shown in table 1.
The test method comprises the following steps:
(1) The gas barrier films prepared in the above examples 1 to 8 and comparative examples 1 to 4 were sequentially compounded with a 15 μm PA film and a 60 μm cast polypropylene film (CPP film) using a high-pressure-cooking two-component polyurethane adhesive, wherein the total thickness of the adhesive was 4 μm, and the prepared packaging composite film had a structure of gas barrier film/adhesive layer/PA film/adhesive layer/CPP film, wherein the barrier layer/silicon oxide layer of the barrier film faced the adhesive layer. Testing the oxygen transmission rate of each composite film according to GB/T19789-2005, and testing the interlayer peeling force of each composite film according to GB/T8808-1988, wherein the interlayer peeling force is particularly the peeling force between the gas barrier film and the PA film;
(2) The gas barrier films obtained in the above examples 1 to 8 and comparative examples 1 to 4 were continuously kneaded and retorted under pressure. The rubbing test is carried out according to GB/T8948, and the conditions are as follows: the angle is 440 degrees, the stroke is 280mm, and the kneading times are 20 times. After kneading, the gas barrier film was placed in a high-pressure cooker and cooked at 121 ℃ for 30min. And (4) after the cooking is finished and the atmosphere is balanced for 24h, carrying out oxygen transmission rate and interlayer peeling force tests according to GB/T19789-2005 and GB/T8808-1988 respectively, wherein the interlayer peeling force refers to the peeling force between the gas barrier film and the PA film.
Table 1 test results before and after kneading and steaming of composite films of examples 1 to 8 and comparative examples 1 to 4
Results and discussion:
combining the test results of examples 1-8 and comparative examples 1-4, it can be seen that before kneading and steaming, the gas barrier films prepared in examples 1-8 and comparative examples 1-4 all have better interlayer peeling force, which is greater than 5N/15mm, but compared with the comparative examples, the gas barrier films obtained in examples 1-8 generally have lower oxygen permeability and relatively better oxygen barrier performance, but after kneading and steaming, the oxygen permeability and interlayer peeling force of the composite films in examples 1-8 are not obviously deteriorated, while the oxygen permeability of the composite films in comparative examples 1, 3 and 4 is obviously increased, the interlayer peeling force is seriously attenuated, and delamination occurs in comparative example 2. Thus, it was demonstrated that the gas barrier film having the barrier layer had relatively better gas barrier properties than the gas barrier film having no barrier layer formed (comparative example 4); the barrier layer/gas barrier film prepared by the coating liquid with the composition and the proportion of the invention has excellent initial gas barrier performance and high interlayer bonding strength, and the gas barrier performance and the interlayer adhesiveness are not obviously deteriorated after the external action of kneading and stewing, and the service performance is stable.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An aqueous coating liquid, characterized by comprising: 100 parts of water-soluble polymer, 10-150 parts of siloxane hydrolysate and nano oxide, 0.1-20 parts of first cross-linking agent, 0.1-10 parts of second cross-linking agent and 1000-12000 parts of solvent, wherein the first cross-linking agent comprises covalent cross-linking agent, and the second cross-linking agent comprises dynamic cross-linking agent.
2. The aqueous coating solution according to claim 1, wherein at least one of the following conditions is satisfied:
the weight ratio of the siloxane hydrolysate to the nano-oxide is 1: (2-50);
the weight ratio of the first cross-linking agent to the second cross-linking agent is (1-10): 1;
the aqueous coating liquid further includes: 0.01-10 parts of auxiliary agent, wherein the auxiliary agent comprises at least one selected from wetting agent, coupling agent, adhesion promoter and flatting agent.
3. The aqueous coating solution according to claim 1 or 2, wherein at least one of the following conditions is satisfied:
the water-soluble polymer includes a hydrophilic functional group, the hydrophilic functional group including a hydroxyl group;
the water-soluble polymer comprises at least one selected from polyvinyl alcohol, starch, cellulose, chitosan, polyacrylic acid, polymaleic anhydride or modified polymers of the above polymers;
the siloxane hydrolyzate comprises Si (OR) 4 Hydrolyzing under acidic condition to obtain product, wherein R is C 1-8 An alkyl group;
the nano oxide comprises at least one selected from alumina, silica, zinc oxide, titanium oxide, zirconia, magnesium carbonate, calcium carbonate and barium sulfate;
the average grain diameter of the nano oxide is 1-100 nm;
the nano oxide is nano particles subjected to surface modification by a coupling agent;
the first cross-linking agent comprises at least one selected from aldehydes, acids, acid anhydrides, amino resins, isocyanates and silane coupling agents;
the second crosslinking agent comprises boric acid and a metal salt;
the solvent comprises water and/or an alcohol.
4. The aqueous coating solution according to claim 3, wherein at least one of the following conditions is satisfied:
the mole percentage content of the hydroxyl in the hydrophilic functional groups of the water-soluble polymer is not less than 80 percent;
the siloxane hydrolyzate is Si (OR) 4 Hydrolyzing the resulting product under acidic conditions at a pH of not more than 4;
the average grain diameter of the nano oxide is 3-50 nm;
the hydroxyl content of the surface of the nano oxide after the surface of the nano oxide is modified by a coupling agent is 1-100 mmol/nm 2 ；
The weight ratio of the boric acid to the metal salt is (1-30): 1;
the metal salt comprises at least one selected from zinc chloride, zinc acetate, ferric chloride, calcium chloride, copper chloride, ferric oxide and sodium chloride;
the second cross-linking agent also comprises a chelating ligand, and the molar ratio of the chelating ligand to the metal salt is (1-4): 1;
the volume ratio of the water to the alcohol in the solvent is (50-1): (1-10).
5. The aqueous coating solution according to claim 4, wherein at least one of the following conditions is satisfied:
in the hydrophilic functional groups of the water-soluble polymer, the mole percentage content of the hydroxyl groups is not less than 85 percent;
the chelating ligand comprises at least one selected from ethylenediamine tetraacetic acid, acetylacetone acetate and ethyl acetoacetate;
the volume ratio of the water to the alcohol in the solvent is (20-1): (1-5).
6. A method for preparing the aqueous coating solution according to any one of claims 1 to 5, comprising:
(1) Mixing a water-soluble polymer, a siloxane hydrolysate, a nano oxide and a solvent according to a predetermined ratio to obtain a mixed solution;
(2) Mixing the mixed solution with a first crosslinking agent and a second crosslinking agent.
7. The method of claim 6, wherein in step (1): dissolving the water-soluble polymer prior to said mixing; and/or, the mixing further comprises: adding the auxiliary agent in a preset ratio.
8. A gas barrier film, comprising:
a base film layer;
a barrier layer provided on at least one surface of the base film layer, the barrier layer being formed using the aqueous coating liquid according to any one of claims 1 to 5 or the aqueous coating liquid obtained by the method according to any one of claims 6 to 7.
9. The gas barrier film of claim 8, satisfying at least one of the following conditions:
the thickness of the base film layer is 5-300 mu m;
the thickness of the barrier layer is 0.05-5 μm;
the base film layer comprises at least one of polyolefin film, polyester film and polyamide film;
the base film layer further includes: the bottom layer is arranged on at least one surface of the base film layer, and the barrier layer is arranged on at least one part of the surface of one side of the bottom layer far away from the base film layer;
the gas barrier film further includes: an inorganic material layer disposed on at least one surface of the base film layer, the barrier layer being disposed on at least a portion of a surface of a side of the base film layer remote from the inorganic material layer.
10. The gas barrier film according to claim 9, wherein the base layer is a bulk layer formed by activating a surface of the base film, or the base layer is a resin layer formed on a surface of the base film;
optionally, the resin layer includes at least one selected from the group consisting of a polyester resin, a polyurethane resin, an acrylic resin, a styrene resin, and an amino resin;
optionally, the thickness of the bottom layer is 0.005-5 μm;
optionally, the inorganic material layer comprises at least one selected from alumina, silica, iron oxide, zirconia, silicon nitride;
optionally, the thickness of the inorganic material layer is 5-500 nm;
optionally, the inorganic material layer includes a plurality of sub-inorganic material layers, the barrier layer includes a plurality of sub-barrier layers, the plurality of sub-inorganic material layers and the plurality of sub-barrier layers are alternately arranged in a direction away from the base film layer, and an outermost layer of the gas barrier film is the sub-barrier layer.
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